CN115536411A - Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof - Google Patents
Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof Download PDFInfo
- Publication number
- CN115536411A CN115536411A CN202211354626.3A CN202211354626A CN115536411A CN 115536411 A CN115536411 A CN 115536411A CN 202211354626 A CN202211354626 A CN 202211354626A CN 115536411 A CN115536411 A CN 115536411A
- Authority
- CN
- China
- Prior art keywords
- parts
- balls
- plate
- bulk density
- petrochemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 49
- 239000010431 corundum Substances 0.000 title claims abstract description 48
- 239000000945 filler Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 239000004568 cement Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002023 wood Substances 0.000 claims abstract description 15
- 150000004645 aluminates Chemical class 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- 239000011362 coarse particle Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 235000012241 calcium silicate Nutrition 0.000 claims description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims 2
- 238000005453 pelletization Methods 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 229910052596 spinel Inorganic materials 0.000 abstract description 6
- 239000011029 spinel Substances 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000011819 refractory material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 235000012245 magnesium oxide Nutrition 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021343 molybdenum disilicide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910017305 Mo—Si Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- -1 barium zirconium aluminate Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5212—Organic
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a plate-shaped corundum ball for high-purity bulk density petrochemical filler and a preparation method thereof, belonging to the technical field of fire resistance and comprising the following raw materials in parts by weight: 70-82 parts of plate-shaped corundum ball base mixture, 4-9 parts of wood reinforcing fiber, 8-12 parts of aluminate cement, 3-7 parts of aluminum oxide, 3-4 parts of silicon dioxide, 3.5-4.5 parts of titanium dioxide and 4-7 parts of calcium carbonate. This high-purity bulk density petrochemical industry is board-like corundum ball for stopping, through multiple raw materials mixture, can improve fire resistance, combine wooden reinforcing fiber to improve structural strength, avoid because the higher cracked phenomenon that leads to of the temperature of sintering, reduce the defective percentage of production, simultaneously, avoid in subsequent use, produce the damage because of the striking, and simultaneously, the use of magnesium spinel improves off-the-shelf purity and bulk density, guarantees off-the-shelf thermal expansion stability, strengthens off-the-shelf outer wall, improves wear resistance.
Description
Technical Field
The invention relates to the technical field of fire resistance, in particular to a plate-shaped corundum ball for high-purity bulk density petrochemical filler.
Background
The refractory material is divided into shaped refractory material and unshaped refractory material, the unshaped refractory material is usually a castable material, is mixed powdery particles consisting of a plurality of aggregates or aggregates and one or more binders, and has strong fluidity and plasticity when being matched with one or more liquids and stirred uniformly.
The plate-shaped corundum is pure sintered corundum which is completely sintered and shrunk without adding additives such as MgO, B2O3 and the like, has a coarse and well-developed alpha-Al 2O3 crystal structure, the content of Al2O3 is more than 99%, the plate-shaped crystal structure has small air holes and more closed air holes, the air porosity is almost equal to that of electric fused corundum, the purity is high, the volume stability is good, and the minimum re-sintering shrinkage is realized.
Bulk density, also known as packing density, refers to the mass per unit volume of a bulk material under specified loading conditions, which is classified into bulk density and tap density depending on the loading conditions, and the mass per unit volume in a natural packing state.
At present, the castable of the ladle used is usually configured by adopting tabular corundum and aluminate cement, in the subsequent use process, the castable of the refractory ladle can expand along with the pouring of molten iron, so that the service life of the castable of the ladle is shortened, and the castable of the ladle is worn along with the storage of the molten iron, so that the outer wall of the castable of the ladle is cracked, and in the subsequent use process, the castable of the ladle is damaged by shaking and impacting, meanwhile, the existing tabular corundum ball is usually formed by firing single alumina, the stacking density is lower, and the actual surface area is lower.
Disclosure of Invention
The invention provides plate-like corundum balls for high-purity bulk density petrochemical fillers and a preparation method thereof. Through multiple raw materials mixture, can improve the fire resistance, combine wooden reinforced fiber to improve structural strength, avoid because the higher cracked phenomenon that leads to of the temperature of sintering, reduce the defective percentage of production, simultaneously, avoid in subsequent use, produce the damage because of the striking, simultaneously, the use of magnesium spinel improves off-the-shelf purity and bulk density, guarantees off-the-shelf thermal expansion stability, strengthens off-the-shelf outer wall, improves resistance to wear.
In order to achieve the above effects, the present invention provides the following technical solutions: the plate-shaped corundum ball for the high-purity bulk density petrochemical filling material comprises the following raw materials in parts by weight: 70-82 parts of plate-shaped corundum ball base mixture, 4-9 parts of wood reinforcing fiber, 8-12 parts of aluminate cement, 3-7 parts of aluminum oxide, 3-4 parts of silicon dioxide, 3.5-4.5 parts of titanium dioxide and 4-7 parts of calcium carbonate.
Further, the plate-shaped corundum ball base mixture comprises 1-3 mm coarse particles and 0.088-1 mm fine powder, and the use ratio of the 1-3 mm coarse particles to the 0.088-1 mm fine powder is controlled.
Furthermore, the length of the wood reinforced fiber is 200-500 μm, the fiber content is 99-99.5%, the bulk density is 90-120 g/L, the water content is less than 5%, the heat resistance is 230 ℃, the combustion loss is 0.3-0.5%, and the pH value is 6-7.5.
Further, the aluminate cement comprises 45-50 parts of calcium aluminate, 50-55 parts of alumina, 5-7 parts of monocalcium aluminate and 2-4 parts of dicalcium silicate.
The method for preparing the plate-shaped corundum balls for the high-purity bulk density petrochemical filler, which is applied to the plate-shaped corundum balls for the high-purity bulk density petrochemical filler in any one of claims 1 to 4, comprises the following steps:
step one, raw material treatment: and (3) grinding the raw materials for preparing the platy corundum balls in a grinder to obtain raw material fine powder.
Step two, converging raw materials: and uniformly mixing the fine powder of the raw materials to obtain the preparation raw material.
Step three, manufacturing green balls: and adding water into the raw materials to prepare raw material mud, and putting the raw material mud into a corresponding balling cylinder to prepare green balls.
Step four, drying: drying the green balls through a drying tower to obtain secondary balls;
step five, sintering: and sintering the secondary balls to obtain balls.
Further, the grinder in the first step is a ceramic ball grinder, the diameter of the ceramic balls arranged in the grinder is 40 mm, and the mesh number of the raw material fine powder is 300 meshes.
Further, in the second step, the rotation speed of mixing the raw material fine powder is 30r/min, and the mixing time is 30-70 min.
Further, in the third step, the specification of the green ball is 2.4cm in diameter, and the ball making time is 2-3 h.
Further, in the step S IV, the drying temperature of the drying tower is 400-500 ℃, the drying time is 18-20 h, and the drying standard water content is 0.4-0.7%.
Further, in the fifth step, sintering equipment is adopted to sinter the secondary balls, the sintering equipment is a natural gas shaft kiln, and the sintering time is 20-22 hours.
The invention provides a plate-shaped corundum ball for high-purity bulk density petrochemical filling material, which has the following beneficial effects:
this high-purity bulk density petrochemical industry is board-like corundum ball for stopping, through multiple raw materials mixture, can improve fire resistance, combine wooden reinforcing fiber to improve structural strength, avoid because the higher cracked phenomenon that leads to of the temperature of sintering, reduce the defective percentage of production, simultaneously, avoid in subsequent use, produce the damage because of the striking, and simultaneously, the use of magnesium spinel improves off-the-shelf purity and bulk density, guarantees off-the-shelf thermal expansion stability, strengthens off-the-shelf outer wall, improves wear resistance.
Drawings
FIG. 1 is a schematic view of the manufacturing method of the present invention.
Detailed Description
The invention provides a technical scheme that: referring to fig. 1, the plate-shaped corundum balls for high-purity bulk density petrochemical fillers comprise the following raw materials in parts by weight: 70-82 parts of plate-shaped corundum ball base mixture, 4-9 parts of wood reinforcing fiber, 8-12 parts of aluminate cement, 3-7 parts of aluminum oxide, 3-4 parts of silicon dioxide, 3.5-4.5 parts of titanium dioxide and 4-7 parts of calcium carbonate.
Specifically, the plate-shaped corundum ball base mixture comprises 1-3 mm coarse particles and 0.088-1 mm fine powder, and the use ratio of the 1-3 mm coarse particles to the 0.088-1 mm fine powder is controlled.
Specifically, the length of the wood reinforced fiber is 200-500 μm, the fiber content is 99-99.5%, the bulk density is 90-120 g/L, the water content is less than 5%, the heat resistance is 230 ℃, the combustion loss is 0.3-0.5%, and the pH value is 6-7.5.
The aluminate cement comprises 45-50 parts of calcium aluminate, 50-55 parts of alumina, 5-7 parts of monocalcium aluminate and 2-4 parts of dicalcium silicate.
The method for preparing the plate-shaped corundum balls for the high-purity bulk density petrochemical filler, which is applied to the plate-shaped corundum balls for the high-purity bulk density petrochemical filler in any one of claims 1 to 4, comprises the following steps:
step one, raw material treatment: and (3) grinding the raw materials for preparing the platy corundum balls in a grinder to obtain raw material fine powder.
Step two, converging raw materials: and uniformly mixing the fine powder of the raw materials to obtain the preparation raw material.
Step three, manufacturing green balls: adding water into the raw materials to prepare raw material mud, and putting the raw material mud into a corresponding balling cylinder to prepare green balls.
Step four, drying: drying the green balls by a drying tower to obtain secondary balls;
step five, sintering: and sintering the secondary balls to obtain balls.
Specifically, the grinder in the first step is a ceramic ball grinder, the diameter of the ceramic balls arranged in the grinder is 40 mm, and the mesh number of the raw material fine powder is 300 meshes.
Specifically, in the second step, the rotation speed of mixing the raw material fine powder is 30r/min, and the mixing time is 30-70 min.
Specifically, in the third step, the diameter of the green ball is 2.4cm, and the ball making time is 2-3 h.
Specifically, in the step S four, the drying temperature of the drying tower is 400-500 ℃, the drying time is 18-20 h, and the drying standard moisture is 0.4-0.7%.
Specifically, in the fifth step, sintering equipment is adopted to sinter the secondary balls, the sintering equipment is a natural gas shaft kiln, and the sintering time is 20-22 h.
The method of the examples was performed for detection analysis and compared to the prior art to yield the following data:
table-one assay
Wear resistance | Bulk density | Resistance to thermal expansion | |
Examples | Is higher than | Is higher than | Is higher than |
Prior Art | Lower is | Lower is | Is lower than |
According to the table data, the high-purity stacking density petrochemical filler plate-shaped corundum balls can improve the fire resistance by mixing various raw materials, improve the structural strength by combining wood reinforced fibers, avoid the cracking phenomenon caused by higher sintering temperature, reduce the defective rate of production, and simultaneously avoid damage caused by impact in the subsequent use process, and meanwhile, the use of magnesium spinel improves the purity and stacking density of finished products, ensures the thermal expansion stability of the finished products, strengthens the outer wall of the finished products, and improves the wear resistance.
The invention provides a plate-shaped corundum ball for high-purity bulk density petrochemical filler, which comprises the following raw materials in parts by weight: 70-82 parts of plate-shaped corundum ball base mixture, 4-9 parts of wood reinforcing fiber, 8-12 parts of aluminate cement, 3-7 parts of aluminum oxide, 3-4 parts of silicon dioxide, 3.5-4.5 parts of titanium dioxide and 4-7 parts of calcium carbonate, wherein the plate-shaped corundum ball base mixture comprises 1-3 mm coarse particles and 0.088-1 mm fine powder, the use ratio of the 1-3 mm coarse particles to the 0.088-1 mm fine powder is controlled, the length of the wood reinforcing fiber is 200-500 mu m, the fiber content is 99-99.5%, the bulk density is 90-120 g/L, the water content is less than 5%, the heat resistance is 230 ℃, the combustion loss is 0.3-0.5%, the PH value is 6-7.5, the aluminate cement comprises calcium aluminate, alumina, monocalcium aluminate and dicalcium silicate, 45-50 parts of calcium aluminate, 50-55 parts of alumina, 5-7 parts of monocalcium aluminate and 2-4 parts of dicalcium silicate, the plate-shaped corundum has good erosion resistance and thermal shock stability, and the main purposes are as follows: firstly, the magnesia-chrome sand is replaced to manufacture the magnesia-alumina spinel brick for a cement rotary kiln, thereby not only avoiding chrome pollution, but also having good anti-stripping property, secondly, the magnesia-chrome sand is used for manufacturing a ladle castable, greatly improving the anti-erosion capability of a steel plate lining, leading the steel plate lining to be widely applied to refractory materials for steelmaking, providing a new raw material for the production of amorphous and shaped high-purity refractory materials by preparing high-quality pre-synthesized spinel, forming a protective film layer on the surface of quartz glass (SiO 2) which is compact by high-temperature combustion in an oxidizing atmosphere so as to prevent the continuous oxidation of molybdenum disilicide, wherein the molybdenum disilicide is an intermediate phase with the highest silicon content in a Mo-Si binary alloy system, is a dalton intermetallic compound with fixed components, has the dual characteristics of metal and ceramic, is a high-temperature material with excellent performance, and has good high-temperature oxidation resistance, the oxidation resistance temperature is higher than 1600 ℃, the product is equivalent to SiC, the product has moderate density (6.24 g/cm), lower thermal expansion coefficient (8.1 multiplied by 10K), good electric thermal conductivity, higher brittle-ductile transition temperature (1000 ℃) and ceramic hard brittleness, the C4AF hundred is distributed among the periclase grains and gradually gathered to the gaps of the included angles of the periclase grains along with the increase of the calcining temperature, so that the high-temperature strength of the brick is improved, the wood reinforcing fiber is organic flocculent fiber substance obtained by chemical treatment and mechanical processing of natural renewable wood, the wood reinforcing fiber is nontoxic, tasteless, pollution-free and nonradioactive, and has excellent flexibility and dispersibility, the lignocellulose is insoluble in water, weak acid and alkaline solution, the pH value is neutral, the corrosion resistance of the rubber compound can be improved, the specific gravity of the lignocellulose is small, the specific surface area is large, and the product has excellent heat preservation property, the heat insulation, sound insulation, insulation and air permeability performances, uniform thermal expansion, no shell and no cracking, the aluminate cement is usually yellow or brown and also gray, and the density and the bulk density of the aluminate cement are similar to those of common portland cement. The fineness is that the specific surface area is more than or equal to 300m < 2 >/kg or the screen residue of a 45 mu m sieve is less than or equal to 20 percent, the aluminate cement comprises three kinds of cement of calcium aluminate, barium aluminate and barium zirconium aluminate, wherein the barium aluminate cement has the characteristics of quick hardening, high strength, high refractoriness and the like, the aluminum oxide is also called STA-1020 abrasive, and the chemical property of silicon dioxide is relatively stable. Does not react with water. The composite material has the advantages of high fire resistance, high temperature resistance, small thermal expansion coefficient, high insulation, corrosion resistance, piezoelectric effect, resonance effect and unique optical characteristics, stable titanium dioxide property, strong adhesion and high melting point, and in the using process, the pH value of the wood reinforced fiber wood in use is correspondingly adjusted according to needs, so that the flexibility in the using process is ensured, and the cracking resistance of the finished product is improved.
The method for preparing the plate-shaped corundum balls for the high-purity bulk density petrochemical filler, which is applied to the plate-shaped corundum balls for the high-purity bulk density petrochemical filler in any one of claims 1 to 4, comprises the following steps: step one, raw material treatment: the raw materials for manufacturing the platy corundum balls are put into a grinding machine for grinding to obtain raw material fine powder, the grinding machine is a ceramic ball grinding machine, the diameter of the ceramic balls arranged in the grinding machine is 40 mm, the mesh number of the raw material fine powder is 300 meshes, the ceramic ball grinding machine improves the production capacity and the crushing efficiency, the application range is also expanded, the ceramic ball grinding machine can provide unrivaled crushing performance in various middle-crushing, fine-crushing and superfine-crushing operations from limestone to basalt and from stone production to various ore crushing, is mainly used for mixing and grinding materials, has uniform fineness of products, saves power, can be used for dry grinding and wet grinding, and can also be used for converging the raw materials in the step two: uniformly mixing the raw material fine powder to obtain a preparation raw material, wherein the mixing speed of the raw material fine powder is 30r/min, the mixing time is 30-70 min, and the step three of preparing green pellets: adding water into the raw materials to prepare raw material mud, putting the raw material mud into a corresponding balling cylinder to prepare green balls, wherein the specification of the green balls is 2.4cm in diameter, the ball preparation time is 2-3 h, and the balling machine is mainly used for pressing powder materials which are difficult to form and is characterized by large forming pressure, adjustable revolution of a main machine, and the matching of a spiral feeding device, the pressure can be adjusted according to the requirement of ball pressing density, the production is flexible, the formed green balls need to have strength, the cracking in the process of transporting to a dryer is avoided, the problems of high water content, easy layering, difficult drying and the like of semi-finished balls in the balling process are avoided, and the step four is drying: drying the green pellets by a drying tower to obtain secondary pellets, wherein the drying temperature of the drying tower is 400-500 ℃, the drying time is 18-20 h, the drying standard water content is 0.4-0.7%, and the step five is sintering: sintering the secondary balls to obtain balls, sintering the secondary balls by adopting sintering equipment, wherein the sintering equipment is a natural gas vertical kiln, the sintering time is 20-22 h, the sintering mode is solid-phase sintering, the powder body generates strength through material migration and causes densification and recrystallization, the sintering temperature is 1900-1950 ℃, a plate corundum structure with full crystal development and sintering is obtained by controlling the temperature and the flow rate of hot air in the vertical kiln, and products with different particle sizes can be obtained after cooling, sorting, inspecting, crushing and screening after sintering, and the sintering is characterized by quick heating and quick cooling.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The plate-shaped corundum ball for the high-purity bulk density petrochemical filler is characterized by comprising the following raw materials in parts by weight: 70-82 parts of plate-shaped corundum ball base mixture, 4-9 parts of wood reinforcing fiber, 8-12 parts of aluminate cement, 3-7 parts of aluminum oxide, 3-4 parts of silicon dioxide, 3.5-4.5 parts of titanium dioxide and 4-7 parts of calcium carbonate.
2. The plate-shaped corundum balls for high-purity packing density petrochemical fillers as claimed in claim 1, wherein the plate-shaped corundum ball base mixture comprises 1-3 mm coarse particles and 0.088-1 mm fine particles, and the use ratio of the 1-3 mm coarse particles to the 0.088-1 mm fine particles is controlled.
3. The plate-like corundum sphere for high purity bulk density petrochemical filler according to claim 1, wherein the wood reinforcing fiber has a length of 200 to 500 μm, a fiber content of 99 to 99.5%, a bulk density of 90 to 120g/L, a water content of < 5%, a heat resistance of 230 ℃, a combustion loss of 0.3 to 0.5%, and a pH of 6 to 7.5.
4. The plate-shaped corundum balls for high-purity bulk density petrochemical filler according to claim 1, wherein the aluminate cement comprises 45-50 parts of calcium aluminate, 5-7 parts of monocalcium aluminate and 2-4 parts of dicalcium silicate, and 45-50 parts of calcium aluminate, and 50-55 parts of aluminum oxide.
5. The method for preparing the plate-like corundum balls for high-purity bulk density petrochemical filler is characterized by being applied to the plate-like corundum balls for high-purity bulk density petrochemical filler, which is disclosed by any one of claims 1 to 4, and comprises the following steps of:
s1, raw material treatment: putting raw materials for manufacturing the platy corundum balls into a grinding machine for grinding to obtain raw material fine powder;
s2, converging raw materials: uniformly mixing the raw material fine powder to obtain a preparation raw material;
s3, preparing a green ball: adding water into the raw materials to prepare raw material mud, and putting the raw material mud into a corresponding balling cylinder to prepare green balls;
s4, drying: drying the green balls through a drying tower to obtain secondary balls;
s5, sintering: and sintering the secondary balls to obtain balls.
6. The method of manufacturing high purity corundum balls for use in petrochemical fillers according to claim 5, wherein the grinding machine in the step S1 is a ceramic ball grinding machine, the diameter of the porcelain balls placed in the grinding machine is 40 mm, and the mesh size of the raw material fine powder is 300 mesh.
7. The method of preparing the plate-shaped corundum balls for high-purity bulk density petrochemical filler according to claim 5, wherein the raw material fine powder is mixed at a rotation speed of 30r/min for 30-70 min in step S2.
8. The method of preparing the plate-like corundum pellets for high purity bulk density petrochemical fillers according to claim 5, wherein the green pellets have a diameter of 2.4cm and the pelletizing time is 2 to 3 hours in step S3.
9. The method for preparing the plate-shaped corundum balls for high-purity bulk density petrochemical fillers as claimed in claim 5, wherein the drying tower is operated at a drying temperature of 400 to 500 ℃ for 18 to 20 hours and a drying standard moisture of 0.4 to 0.7% in step S4.
10. The method of claim 5, wherein the secondary balls are sintered in step S5 using a sintering apparatus, wherein the sintering apparatus is a natural gas shaft kiln, and the sintering time is 20 to 22 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211354626.3A CN115536411A (en) | 2022-11-01 | 2022-11-01 | Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211354626.3A CN115536411A (en) | 2022-11-01 | 2022-11-01 | Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115536411A true CN115536411A (en) | 2022-12-30 |
Family
ID=84720877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211354626.3A Pending CN115536411A (en) | 2022-11-01 | 2022-11-01 | Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115536411A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116874288A (en) * | 2023-06-16 | 2023-10-13 | 辽宁煜鑫高科技术新材料有限公司 | Preparation method and application of platy corundum sphere refractory material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104909772A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Composite additive containing calcium aluminate cement combined corundum castable and preparation method thereof |
CN104909771A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Calcium aluminate cement-combined corundum castable and preparation method thereof |
CN104909773A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Composite-additive-containing calcium-aluminate-cement-bound aluminum magnesium castable and preparation method thereof |
WO2021147411A1 (en) * | 2020-01-20 | 2021-07-29 | 武汉科技大学 | Phase change heat storage self-flowing refractory castable and preparation method therefor |
CN114394840A (en) * | 2021-12-31 | 2022-04-26 | 江苏新时高温材料股份有限公司 | Plate-shaped corundum ball for high-purity bulk density petrochemical filler |
CN114477972A (en) * | 2021-12-30 | 2022-05-13 | 江苏新时高温材料股份有限公司 | Large-granularity plate-shaped corundum for large-sized ladle castable |
-
2022
- 2022-11-01 CN CN202211354626.3A patent/CN115536411A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104909772A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Composite additive containing calcium aluminate cement combined corundum castable and preparation method thereof |
CN104909771A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Calcium aluminate cement-combined corundum castable and preparation method thereof |
CN104909773A (en) * | 2015-06-03 | 2015-09-16 | 武汉科技大学 | Composite-additive-containing calcium-aluminate-cement-bound aluminum magnesium castable and preparation method thereof |
WO2021147411A1 (en) * | 2020-01-20 | 2021-07-29 | 武汉科技大学 | Phase change heat storage self-flowing refractory castable and preparation method therefor |
CN114477972A (en) * | 2021-12-30 | 2022-05-13 | 江苏新时高温材料股份有限公司 | Large-granularity plate-shaped corundum for large-sized ladle castable |
CN114394840A (en) * | 2021-12-31 | 2022-04-26 | 江苏新时高温材料股份有限公司 | Plate-shaped corundum ball for high-purity bulk density petrochemical filler |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116874288A (en) * | 2023-06-16 | 2023-10-13 | 辽宁煜鑫高科技术新材料有限公司 | Preparation method and application of platy corundum sphere refractory material |
CN116874288B (en) * | 2023-06-16 | 2024-04-16 | 辽宁煜鑫高科技术新材料有限公司 | Preparation method and application of platy corundum sphere refractory material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106588059B (en) | Prefabricated member for lime rotary kiln and preparation method thereof | |
CN106145976B (en) | Andalusite-mullite-silicon carbide brick for cement kiln and preparation method thereof | |
CN106938922B (en) | Silicon corundum abrasive brick | |
CN108975923B (en) | Ceramic roller rod with thermal shock resistance and high-temperature volume stability and preparation method thereof | |
CN107117976A (en) | A kind of transition band of cement kiln Mg-Al spinel brick and preparation method thereof | |
JP2021502941A (en) | A method for producing a porous sintered magnesia, a batch for producing a crude ceramic (grobkeramisch) refractory product having a granulated product (Koernung) made of sintered magnesia, such a product, and a product. Method of manufacture, lining of industrial furnace (Zustellung), and industrial furnace | |
CN106938923B (en) | Silicon corundum wear-resistant composite brick | |
CN110563476A (en) | Fiber-reinforced refractory brick and preparation method thereof | |
CN112456974B (en) | Magnalium spinel brick for co-processing cement kiln and preparation method and application thereof | |
CN111362676A (en) | High-wear-resistance quick-drying refractory castable and preparation method thereof | |
CN102249655B (en) | Ductile mullite brick for pipelines of hot blast stoves and manufacturing method thereof | |
JP5943032B2 (en) | Manufacturing method of lightweight heat-insulating alumina / magnesia refractory | |
CN108484139B (en) | Preparation method of magnesium-chromium refractory material | |
CN113443898A (en) | Low-thermal-conductivity spinel refractory homogeneous brick and preparation method and application thereof | |
CN115536411A (en) | Plate-shaped corundum ball for high-purity bulk density petrochemical filler and preparation method thereof | |
JPH08283073A (en) | Kiln tool | |
CN114163228B (en) | Slag-stopping sliding plate of aluminum-calcium-carbon converter and preparation method thereof | |
EP4059910A1 (en) | Mag-galaxite spinel refractory material and preparation method and use thereof | |
CN111018500A (en) | Preparation method of high-purity alumina ceramic and preparation method of ceramic product | |
CN106946550B (en) | A kind of magnesia-spinel brick and preparation method thereof that antistrip performance is excellent | |
CN112897994A (en) | Preparation method of corundum spinel complex phase material | |
CN110615670A (en) | High-performance magnesium sliding brick and preparation method thereof | |
JP2004292230A (en) | Wear resistant alumina sintered compact and method of manufacturing the same | |
CN114477972A (en) | Large-granularity plate-shaped corundum for large-sized ladle castable | |
CN114394840A (en) | Plate-shaped corundum ball for high-purity bulk density petrochemical filler |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221230 |
|
RJ01 | Rejection of invention patent application after publication |